Discriminating the regional and urban contributions in the North-Western Mediterranean: PM levels and composition

Simultaneous measurements of the PM concentration levels and chemical composition of atmospheric aerosols at a regional background (RB) and an urban background (UB) site, located in the same geographic region, allowed for the determination of their urban and regional contributions. In the specific case of the North-Western region of the Mediterranean the RB amount has been quantified in 18, 13 and 12 μg m^?3 for PM₁₀, PM_2.5 and PM₁, respectively, whereas the UB contribution reached 22, 13 and 8 μg m^?3, respectively. The UB contributions in the Western Mediterranean are much higher than those observed in other European regions; especially concerning the coarse fraction. The high loads of road dust in the urban areas across the Mediterranean may account for these large differences.The urban contributions are extremely enriched in Ca, Fe, Sb, Sn, Cu, Zn, being the main tracers of the road dust, with concentrations up to 6–8 times higher than those at the RB. Elemental carbon and nitrate are mainly derived from direct vehicular emissions. Some industrial tracers (Mn, Pb, Bi) are also enriched in the urban area. The evaluation of the Cu/Sb, Cu/Zn, Cu/Cd and Cu/Pb ratios and the high enrichment of these trace elements versus the Upper Crustal Composition average values corroborates the importance of the road-traffic emissions in the study area, also influencing the RB.The supplementary results from a suburban site in the Balearic Islands and the evaluation of the V/Ni ratios evidence the strong signature of fuel-oil combustion processes, which is a general characteristic of the Mediterranean aerosols.     

Determination of sixteen pesticides in peppers using high-performance liquid chromatography/mass spectrometry

A method for the detection and quantification of 16 pesticides: flufenoxuron, fenoxycarb, dimethomorph, acetamiprid, imidacloprid, lufenuron, thiacloprid, thiabendazole, thiophanate-methyl, spinosad, fenbutatin oxide, methoxyfenozide, oxamyl, clothianidin, thiamethoxam and carbendazim has been developed based on high-performance liquid chromatography-mass spectrometry. Pesticide residues were extracted from the samples according to the QuEChERS method which stands for quick, essay, cheap, effective, rugged and safe. Homogenised analytical portions (10 g ± 0.1) of samples of peppers were spiked at two levels (10 and 100 μg kg?1) with a small volume of an appropriate standard mixture solution containing each pesticide. Analyses were performed using electrospray ionization (ESI) and a MSD trap system. Chromatography separation was achieved using a ZORBAX SB-C18 3.5 μm particle size analytical column, 2.1 × 50 mm from Agilent, with gradient elution at a flow-rate of 0.4 mL/min with mobile phases: waters-0.1 % HCOOH-5 mM HCOONH? and MeOH-5 mM HCOONH?. The method has been validated based on the SANCO European Guidelines. Under the optimized conditions the recoveries (n = 7) were in the range 70-110 % with satisfactory precision (CV ≤ 20 %). A linear dynamic range was obtained over a range of concentrations from 10 to 100 μg kg?1 for each of the analytes, with correlation coefficients >0.997.     

A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations

The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM₁₀ composition were obtained. Based on these datasets, the mean PM₁₀ compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM₁₀ concentrations was completed. Subsequently, the estimated PM₁₀ composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.     

Biosorption of zinc ions from aqueous solution by the microalga Scenedesmus obliquus

Aquatic environments are often exposed to toxic heavy metals, which gain access to the food chain via microalgae and may cause severe problems at higher trophic levels. However, such a metabolic specificity can be taken advantage of in bioremediation strategies. The potential of a novel wild strain of Scenedesmus obliquus, previously isolated from a heavy metal-contaminated site in northern Portugal, to remove Zn from aqueous solutions was thus studied, using several initial concentrations. The removal extent reached its maximum by 1 day: 836.5 mg Zn/g biomass, at the initial concentration of 75 mg/L, mainly by adsorption onto the cell surface. Comparative studies encompassing a commercially available strain of the same microalgal species led to a maximum removal extent of only 429.6 mg Zn/g biomass, under identical conditions. Heat-inactivated cells permitted a maximum removal of 209.6 mg Zn/g biomass, at an initial concentration of 50 mg Zn/L. The maximum adsorption capacity of Zn, estimated via Langmuir’s isotherm, was 330 mg Zn/g biomass. Finally, Zn removal was highest at pH 6.0–7.0. It was proven, for the first time, that such a wild microalga can uptake and adsorb Zn very efficiently, which unfolds a particularly good potential for bioremediation. Its performance is far better than similar (reference) species, especially near neutrality, and even following heat-treatment.     

Influence of sediment composition on PAH toxicity using zebrafish (Danio rerio) and Japanese medaka (Oryzias latipes) embryo-larval assays

Due to hydrophobic and persistent properties, polycyclic aromatic hydrocarbons (PAHs) have a high capacity to accumulate in sediment. Sediment quality criteria, for the assessment of habitat quality and risk for aquatic life, include understanding the fate and effects of PAHs. In the context of European regulation (REACH and Water Framework Directive), the first objective was to assess the influence of sediment composition on the toxicity of two model PAHs, benzo[a]pyrene and fluoranthene using 10-day zebrafish embryo-larval assay. This procedure was undertaken with an artificial sediment in order to limit natural sediment variability. A suitable sediment composition might be then validated for zebrafish and proposed in a new OECD guideline for chemicals testing. Second, a comparative study of toxicity responses from this exposure protocol was then performed using another OECD species, the Japanese medaka. The potential toxicity of both PAHs was assessed through lethal (e.g., survival, hatching success) and sublethal endpoints (e.g., abnormalities, PMR, and EROD) measured at different developmental stages, adapted to the embryonic development time of both species. Regarding effects observed for both species, a suitable artificial sediment composition for PAH toxicity testing was set at 92.5 % dry weight (dw) silica of 0.2–0.5-mm grain size, 5 % dw kaolin clay without organic matter for zebrafish, and 2.5 % dw blond peat in more only for Japanese medaka. PAH bioavailability and toxicity were highly dependent on the fraction of organic matter in sediment and of the K _ow coefficients of the tested compounds. The biological responses observed were also dependent of the species under consideration. Japanese medaka embryos appeared more robust than zebrafish embryos for understanding the toxicity of PAHs following a sediment contact test, due to the longer exposure duration and lower sensitivity of sediment physical properties.     

Air stripping of ammonia from pig slurry: characterisation and feasibility as a pre- or post-treatment to mesophilic anaerobic digestion

The objective of the present paper has been to study the effect of pig slurry waste type, fresh or anaerobically digested, and the effect of initial pH on ammonia air stripping from pig slurry waste at high temperature (80 degrees C). Stripping process as pre- or post-treatment to anaerobic digestion has been also evaluated. Treatment performances differ according to pig slurry type. When fresh pig slurry is used, despite working at 80 degrees C, a high initial pH (11.5) is required for complete ammonia removal. On the other hand, for digested pig slurry, complete ammonia removal without pH modification is possible and organic matter significantly less contaminates recovered ammonia salt. Batch anaerobic tests showed that ammonia air stripping is not an advisable pre-treatment to pig slurry anaerobic digestion.     

Assessing instruments for mixed household solid waste collection services in the Flemish region of Belgium

Instruments to reduce waste can be divided into three groups: first, pecuniary incentives; second, service level; finally, measurements stimulating prevention and waste reduction. Also specific characteristics of the community determine the amount of waste generated. We evaluate whether findings in literature on effectiveness of policy measures are valid for Belgium, specifically for the Flemish region. The policy mix instituted by the Flemish authorities in the ‘implementation plan household waste 2003–2007’ and implemented by local authorities, is assessed. Multiple regression analysis identifies those measurements having the greatest impact on household solid waste.We found an income elasticity of 0.326. Also the provided service level has a significant impact. Pecuniary incentives are effective instruments in reducing waste, with a price elasticity of −0.139. Furthermore, a higher percentage of direct costs, directly attributable to waste services, borne by households, reduces waste. A consequent implementation of the ‘polluter pays’ principle proves to be effective.     

Workplace aerosol mass concentration measurement using optical particle counters

Direct-reading aerosol measurement usually uses the optical properties of airborne particles to detect and measure particle concentration. In the case of occupational hygiene, mass concentration measurement is often required. Two aerosol monitoring methods are based on the principle of light scattering: optical particle counting (OPC) and photometry. The former analyses the light scattered by a single particle, the latter by a cloud of particles. Both methods need calibration to transform the quantity of scattered light detected into particle concentration. Photometers are simpler to use and can be directly calibrated to measure mass concentration. However, their response varies not only with aerosol concentration but also with particle size distribution, which frequently contributes to biased measurement. Optical particle counters directly measure the particle number concentration and particle size that allows assessment of the particle mass provided the particles are spherical and of known density. An integrating algorithm is used to calculate the mass concentration of any conventional health-related aerosol fraction. The concentrations calculated thus have been compared with simultaneous measurements by conventional gravimetric sampling to check the possibility of field OPC calibration with real workplace aerosols with a view to further monitoring particle mass concentration. Aerosol concentrations were measured in the food industry using the OPC GRIMM? 1.108 and the CIP 10-Inhalable and CIP 10-Respirable (ARELCO?) aerosol samplers while meat sausages were being brushed and coated with calcium carbonate. Previously, the original OPC inlet had been adapted to sample inhalable aerosol. A mixed aerosol of calcium carbonate and fungi spores was present in the workplace. The OPC particle-size distribution and an estimated average particle density of both aerosol components were used to calculate the mass concentration. The inhalable and respirable aerosol fractions calculated from the OPC data are closely correlated with the results of the particle size-selective sampling using the CIP 10. Furthermore, the OPC data allow calculation of the thoracic fraction of workplace aerosol (not measured by sampling), which is interesting in the presence of allergenic particles like fungi spores. The results also show that the modified COP inlet adequately samples inhalable aerosol in the range of workplace particle-size distribution.     

Shifts in Microbial Communities, Microbial Biomass and Organic Matter Mineralization for Three Mediterranean Soils Contaminated By Metals

Microbial communities (phospholipid fatty acid pattern, bacterial growing strategies, eco-physiological index (EPI) and total bacteria counts, as a number of heterotrophic cuhurable bacteria), substrate-induced respiration (SIR), and nitrogen mineralization were studied in three Mediterranean soils at three different depth levels (A, B and C). Soils were experimentally treated with a final concentration of 1000 ppm of trace metals (Cu²⁺, Zn²⁺, Al³⁺, Fe²⁺, Pb²⁺, Ni²⁺, Mn²⁺, Cr³⁺ and Cd²⁺). Soils were stored in 571 plastic containers for one year, and watered with 1001 during this period. Leachate was recovered through a bottom tap. Samples of the three depths were studied. Soil microbial communities showed different effects to other studies presented in the literature, but carried out on non-Mediterranean soils. Dramatic differences were found between treated soils and untreated ones, but not between soils or horizons. the treated soil displayed a decrease in CFUs, SIR N-mineralization and EPI together with a dominance of r-growing strategists. the relative moles percent of several PLFAs, especially 15:0, 16: 1ω7, cy17: 0, br18:0 and 18: 1ω7 decreased because of the pollution of soils, whereas 10Me16, 18:2ω6, cy19:0, i16:0 and br17:0 showed higher values than in untreated soils.     

Rate of occurrence of failures based on a nonhomogeneous Poisson process: an ozone analyzer case study

Atmospheric pollutant monitoring constitutes a primordial activity in public policies concerning air quality. In São Paulo State, Brazil, the São Paulo State Environment Company (CETESB) maintains an automatic network which continuously monitors CO, SO₂, NO _x , O₃, and particulate matter concentrations in the air. The monitoring process accuracy is a fundamental condition for the actions to be taken by CETESB. As one of the support systems, a preventive maintenance program for the different analyzers used is part of the data quality strategy. Knowledge of the behavior of analyzer failure times could help optimize the program. To achieve this goal, the failure times of an ozone analyzer—considered a repairable system—were modeled by means of the nonhomogeneous Poisson process. The rate of occurrence of failures (ROCOF) was estimated for the intervals 0–70,800 h and 0–88,320 h, in which six and seven failures were observed, respectively. The results showed that the ROCOF estimate is influenced by the choice of the observation period, t ₀?=?70,800 h and t ₇?=?88,320 h in the cases analyzed. Identification of preventive maintenance actions, mainly when parts replacement occurs in the last interval of observation, is highlighted, justifying the alteration in the behavior of the inter-arrival times. The performance of a follow-up on each analyzer is recommended in order to record the impact of the performed preventive maintenance program on the enhancement of its useful life.